Efficient and Bio‐inspired Conversion of Cellulose to Formic Acid Catalyzed by Metalloporphyrins in Alkaline Solution

Abstract

A bio-inspired approach for efficient conversion of cellulose to formic acid (FA) was developed in an aqueous alkaline medium. Metalloporphyrins mimicking cytochrome P450 exhibit efficiently and selectively catalytic performance in catalytic conversion of cellulose. High yield of FA about 63.7% was obtained by using sulfonated iron(III) porphyrin as the catalyst and O 2 as the oxidant. Iron(III)-peroxo species, TSPPFe III OO  , was involved to cleave the C-C bonds of gluconic acid to FA in this catalytic system. This approach used relatively high concentration of cellulose and ppm concentration of catalyst. This work may provide a bio-inspired route to efficient conversion of cellulose to FA.

Towards Sustainable Production of Formic Acid

“…Liu et al used ab ioinspired conversion of cellulose with sulfonated iron(III)-porphyrina s the catalystina na queous solution of NaOH with O 2 (2 MPa) as the oxidant,a nd obtained ay ield of 64 %f or formic acid at 423 K. [57] Liu et al used ab ioinspired conversion of cellulose with sulfonated iron(III)-porphyrina s the catalystina na queous solution of NaOH with O 2 (2 MPa) as the oxidant,a nd obtained ay ield of 64 %f or formic acid at 423 K. [57] …”

“…Alkalis can also be used insteado fa cids for the first step of cellulose conversion:h ydrolysis. Liu et al used ab ioinspired conversion of cellulose with sulfonated iron(III)-porphyrina s the catalystina na queous solution of NaOH with O 2 (2 MPa) as the oxidant,a nd obtained ay ield of 64 %f or formic acid at 423 K. [57]…”

Catalytic Oxidation of Biomass to Formic Acid Using O2 as an Oxidant

“…Hence, Keggintype HPAs have been broadly used in the oxidation of biomass to FA due to their good catalytic performance. 32 In 2011, Wasserscheid et al 33 first applied a Keggin-type HPA, H 5 PV 2 Mo 10 O 40 , as a catalyst in the oxidation of a biomass model compound, glucose, in aqueous solutions at temperatures from 60 to 90 °C under 0.10 MPa O 2 . The product is only FA, and the byproduct is CO 2 .…”

“…Bioinspired Catalysts. Inspired by nature, Guo et al 32 developed a metalloporphyrins mimicking cytochrome P450 catalyst (TSPPFeCl) and used it to selectively oxidize cellulose to FA in an aqueous alkaline solution. Cellulose was fully converted to FA in an aqueous NaOH solution using TSPPFeCl as a catalyst at 150 °C and 2.0 MPa of O 2 and a high yield of 63.7% was obtained.…”

Iron porphyrin-catalyzed N-trifluoroethylation of anilines with 2,2,2-trifluoroethylamine hydrochloride in aqueous solution

“…18 However, except for our patent, 19 metalloporphyrin-based N-H insertion with triuoroethylamine hydrochloride as the carbene precursor have not been explored to date. In view of the importance of N-triuoroethylated anilines and also as part of our ongoing interest in metalloporphyrin-based biomimetic catalysis, [20][21][22][23][24] herein, we report one-pot method for iron-porphyrin catalyzed N-triuoroethylation of amines with triuoroethylamine hydrochloride as the uorine source in aqueous solution, as described in Scheme 1d.…”